Shelf life and color profile of resin compositions with silver nanoparticles

ABSTRACT

Methods of forming antimicrobial resin compositions comprising silver nanoparticles are disclosed, wherein the resin compositions that are generated exhibit lower initial color, reduced color shift upon storage and reduced levels of spontaneous polymerization. Such methods generally comprise: combining a silver-containing material with a self-cure and dual-cure base resin in situ wherein the base resin does not contain a catalytic amine; and adding a catalytic resin to the mixture of the resin and silver-containing material in order to form the final cured resin. Antimicrobial polymeric materials formed by said methods are also disclosed.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.15/026,970, filed on Apr. 2, 2016. U.S. patent application Ser. No.15/026,970 is a U.S. National Stage Application of PCT/US14/58927, filedon Oct. 2, 2014. PCT/US14/58927 claims priority to U.S. ProvisionalPatent Application No. 61/885,637 filed Oct. 2, 2013, which isincorporated herein by reference in its entirety as if fully set forthherein. This Application incorporates by reference, the entirety of U.S.patent application Ser. No. 13/162,454 filed Jun. 16, 2011.

TECHNICAL FIELD

This invention relates to a resin composition comprising silverparticles that exhibits antimicrobial properties and improved shelf lifecolor stability.

BACKGROUND OF THE INVENTION

Resin based restorative materials are the material of choice by doctorsand patients due to their good mechanical properties, biocompatibilityand aesthetic properties. A resin-based composition that possessesantimicrobial properties and inhibits microbial growth would bedesirable. The applications that such an antimicrobial resin could beuseful in include, products that can be used in medical applicationsincluding orthopedic applications and dental applications such as dentalcements, luting agents and restorative materials. Various antibacterialagents have been incorporated into dental products such as rinsesolutions, toothpastes, coatings, and dental resins to kill bacteria orinhibit bacterial growth, as well as in medical and other commercialproducts. Silver has been shown to be an effective antibacterial agent.However silver-based compositions often tend to be colored (“yellow” to“amber”) and then “darken” or “blacken” upon storage and degrade theaesthetic appearance of these compositions rendering the materialinapplicable to many products. Therefore, it would be desirable tocreate a silver-based resin composition that displays the antimicrobialproperties of silver without the associated coloring and/or darkening orblackening.

SUMMARY OF THE INVENTION

An embodiment of the invention is directed to an antimicrobial resincomposition containing silver particles and having a lower initial color(less yellow, more white) and reduced color shift, i.e., change in colorover time.

A further embodiment of the invention is directed to methods for makingan antimicrobial resin composition containing silver particles andhaving a lower initial color and reduced color shift over time.

Another embodiment of the invention is directed to a method for makingan antimicrobial resin composition wherein a silver compound is mixedinto the base resin (which contains the self-cure initiator) and storedin the dark or under “yellow light” prior to and during mixing with thecatalyst resin.

Other embodiments of the invention are directed to methods of storingthe cured resin in the dark or under “yellow light” to reduce colorshift.

The foregoing has outlined rather broadly the features of the presentdisclosure in order that the detailed description that follows may bebetter understood. Additional features and advantages of the disclosurewill be described hereinafter, which form the subject of the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the change in color of a silver benzoate solution overtime;

FIG. 2 shows the change in color of a catalyst resin;

FIG. 3 shows the darkening and spontaneous self-polymerization of acatalyst resin;

FIG. 4 shows the initial color of the base resin with benzoyl peroxide(A); the catalyst resin that contains photoinitiators (B), and catalystresin with amine and silver benzoate (C);

FIG. 5 shows the color shift of the resin over time after the mixture ofsilver benzoate containing DMAEMA and the catalyst resin is mixed withthe base resin and polymerized at the time of mixing (A); after 30seconds (B); and after less than one (1) minute (C);

FIG. 6 a sample of the resin after polymerization is complete;

FIGS. 5-6 demonstrate the color shift of the resin after the mixture ofsilver benzoate containing DMAEMA and the catalyst resin is mixed withthe base resin and polymerized;

FIG. 7 shows the color profile of various resin compositions prepared byadding the silver benzoate/DMAEMA mixture to the catalyst resin portion;

FIG. 8 shows the color profile of various resin compositions prepared byadding the silver benzoate/DMAEMA mixture to the base resin portion;

FIG. 9 compares the resin compositions of FIG. 7 (A) with the colorprofiles of various resin compositions prepared with the silverbenzoate/DMAEMA mixture added to the base resin before mixing with thecatalyst resin to polymerize and cured by either light-curing orself-curing (B);

FIG. 10 demonstrates the effects of light on resin samples in the dark(A) and in the light (B);

FIG. 11 demonstrates the effects of light on resin samples in the light(A) and in the dark (B); and

FIG. 12 demonstrates the reduced color shift of various resincompositions prepared in accordance with embodiments of the claimedinvention, self-cured, and stored in the dark.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

In the following description, certain details are set forth so as toprovide a thorough understanding of the present embodiments disclosedherein. However, it will be understood by those skilled in the art thatthe present disclosure may be practiced without such specific details.In many cases, details concerning such considerations and the like havebeen omitted inasmuch as such details are not necessary to obtain acomplete understanding of the present disclosure and are within theskills of persons of ordinary skill in the relevant art.

The definitions and explanations as set forth herein are meant andintended to be controlling in any future construction unless clearly andunambiguously modified in the following Description or when applicationof the meaning renders any construction meaningless or essentiallymeaningless. In cases where the construction of the term would render itmeaningless or essentially meaningless, the definition should be takenfrom Webster's Dictionary, 3rd Edition. Definitions and/orinterpretations should not be incorporated from other patentapplications, patents, or publications, related or not, unlessspecifically stated in this specification or if the incorporation isnecessary for maintaining validity.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of components used herein are to beunderstood as modified in all instances by the term “about”.

The present disclosure pertains to methods of forming antimicrobialresin compositions that comprise in situ generated silver nanoparticles.In some embodiments, the resin compositions are formed by combining asilver-containing material with a resin in situ and then curing theresin in the presence of the silver-containing material. Other aspectsof the present disclosure pertain to antimicrobial resin compositionsthat comprise the above-mentioned in situ generated silvernanoparticles.

As used herein, the term, “antimicrobial” means that the articleexhibits one or more of the following properties: the inhibition of theadhesion of bacteria or other microbes to the article; the inhibition ofthe growth of bacteria or other microbes on the article; and/or thekilling of bacteria or other microbes on the surface of the article orin an area surrounding the article. For purposes of this invention,adhesion of bacteria or other microbes to the article, the growth ofbacteria or other microbes on the article and the presence of bacterialor other microbes on the surface of the article are collectivelyreferred to as “microbial colonization.” In various embodiments, thearticles of the present disclosure exhibit varying levels of inhibitionof viable bacteria or other microbes. Such bacteria or other microbesinclude but are not limited to Pseudomonas aeruginosa, Acanthamoebaspecies, Staphyloccus aureus, Escherichia coli, Staphyloccusepidermidis, Serratia marcesens, Acinetobacter baumannii and/or thelike.

As used herein, the term “patient” means and refers to a human oranimal. Suitable examples include, but are not limited to a human or ananimal (e.g., a dog, a cat, a horse, a bird, a reptile, an amphibian, afish, a turtle, a guinea pig, a hamster, a rodent, a cow, a pig, a goat,a primate, a monkey, a chicken, a turkey, a buffalo, an ostrich, asheep, a llama).

As used herein, the term “chemically feasible” refers to a connectivityof atoms such that the chemical valency of each atom is satisfied. Forexample, an oxygen atom with two bonds and a carbon atom with four bondsare chemically feasible.

As used herein, the term “nanoparticle(s)” means and refers to smallparticles ranging from small visible particles to particles on thenano-scale. As used herein, the term “metallic nanoparticle(s)” meansand refers to nanoparticles that contain one or more metals, such assilver.

As used herein, the term “polymeric” means and refers to acomposition(s) that comprises one or more monomers, oligomers, polymers,copolymers, or blends thereof. Suitable examples of polymers include,but are not limited to, polyvinyl alcohol, poly ethylene glycol, ethylcellulose, polyolefins, polyesters, nonpeptide polyamines, polyamides,polycarbonates, polyalkenes, polyvinyl ethers, polyglycolides, celluloseethers, polyvinyl halides, polyhydroxyalkanoates, polyanhydrides,polystyrenes, polyacrylates, polymethacrylates, polyurethanes,polypropylene, polybutylene terephthalate, polyethylene terephthalate,nylon 6, nylon 6,6, nylon 4,6, nylon 12, phenolic resins, urea resins,epoxy resins, silicone polymers, polycarbonates, polyethylenevinylacetate, polyethylene ethyl acrylate, polylactic acid,polysaccharides, polytetrafluoroethylene, polyvinylidenes,polyphosphazines, chlorinated polyethylenes, polysulfones and copolymersand blends thereof. It is also noted that the terms “polymeric”,“polymer” and “resin” may be used interchangeably in the presentdisclosure.

As used herein, the term “water soluble” or use of the term “miscible inwater” means and refers to a level of solubility such that when acomposition is placed in water, greater than about 2.0 percent by weightof the composition dissolves. For example, methyl methacrylate (MMA) isconsidered substantially non water soluble, yet has a water solubilityof about 1.6 g in 100 g of water.

Currently, polymeric materials, such as polymethyl methacrylate (PMMA),are used in many industries for numerous purposes. For instance,polymeric resin materials are used in dentistry, orthopedics andcraniofacial surgery. However one major problem with the utilization ofpolymeric resin materials is the occurrence of infections (e.g., cariesin dentistry). For example, but not by way of limitation, approximately10% of soldiers returning from various battlefields develop infectionsafter receiving craniofacial implants. Likewise, failure of orthopedicimplants is often due to the periprosthetic infections of the PMMA bonecement. Current therapies to treat the more severe cases of infectionsinvolve the use of local and systemic antibiotics. However, antibiotictherapy poses the problem of generating resistant strains of bacteria.In the military, this is of special concern because many troopsreturning from various battlefields are infected with Acinetobacterbaumannii, a multi-antibiotic resistant bacteria. Resin compositions ofthe claimed invention are also applicable in dental applications such asdental cements, luting agents and restorative materials. Furthermore,resin compositions of the claimed invention can be used in non-medicalcommercial applications as well.

Accordingly, antimicrobial agents have been added to many polymericmaterials in order to prevent infections during their various uses. Forinstance, silver salts have been used in human healthcare and medicineas an antiseptic for post surgical infections. Silver salts have alsobeen used as an anti-microbial agent for various purposes in dentaldevices, wound therapy, medical devices, and/or the like. Specifically,silver nitrate has been used to prevent ophthalmic neonatorum innewborns.

However, as discussed previously silver particle-containing polymerstend to be colored and/or tend to darken or blacken during storage andthus, tend to lose their aesthetic appeal. Accordingly, novel methods offorming antimicrobial polymeric materials and novel resulting productsand compositions of matter that have improved shelf life and colorprofile relative to existing silver containing resin compositions havebeen developed. In some embodiments, the present disclosure providesmethods of forming an antimicrobial resin composition that comprises asilver nanoparticle. Such methods generally comprise: combining asilver-containing material with a resin in situ wherein the resin doesnot contain a catalytic amine; and adding a catalytic resin to themixture of the resin and silver-containing material in order to form thefinal cured resin.

By generating the metallic nanoparticle in situ, the monomercompositions can be cured more effectively with better nanoparticledispersion than the prior art.

As explained below, numerous metal containing materials and resins maybe used in various embodiments of the present disclosure. Likewise,various curing methods may be used to form the polymeric materials ofthe present disclosure.

Silver Containing Materials

A person of ordinary skill in the art will recognize that various silvercontaining materials may be used with the methods and compositions ofthe present disclosure. Specific examples include silver-containingmaterials (e.g., silver, silver alloys, silver oxides, silver carbides,silver nitrides, silver borides, silver borate, silver sulfides, silvermyristates, silver stearates, silver oleates, silver gluconates, silveradipates, silver silicates, silver phosphides, silver halides, silverhydrides, silver nitrates, silver carbonates, silver sulfadiazines,silver acetates, silver lactates, silver citrates, alkali silverthiosulphates (e.g., sodium silver thiosulphate, potassium silverthiosulphate)).

In some embodiments, the silver containing materials are soluble inorganic solvents and acrylic monomers. In more specific embodiments,metal containing materials may be silver oleates, silver gluconates,silver adipates, silver sulfadiazines, silver acetates, silver benzoateand the like. In further embodiments, the metal containing material issilver benzoate.

Resins

A person of ordinary skill in the art will also recognize that variousresins may be used with the methods and compositions of the presentdisclosure. Non-limiting examples include acrylic resins. Acrylic resinsinclude, but are not limited to, any resin containing an acrylate group(═CR—COOR′), where R and R′ can be hydrogen, methyl, ethyl, butyl,benzoyl, or any alkyl or aryl group that is chemically feasible.

Other examples of resins that may be used with various embodiments ofthe present disclosure includes poly (methyl methacrylate) (PMMA) resins(an oil-based acrylic resin), other oil-based resins, water solubleresins, and/or the like.

More specific examples of resins that can be used with variousembodiments of the present disclosure include, without limitation:Bis-GMA (bisphenol glycidyl methacrylate) based resins; TEGDMA(triethylene glycol dimethacrylate) based resins; HEMA (2-hydroxyethylmethacrylate) based resins; PMDM (pryomellitic acid diethylmethacrylate)based resins; PMGDM (pyromellitic acid glycerol dimethacrylate) basedresins; UDMA (urethane dimethacrylate) based resins; methacrylate basedresins; dimethacrylate based resins; hydrophobic resins; hydrophilicresins; and hardenable monomers suitable for dental and orthopedicapplications.

Generally, oil-based resins are not soluble in water or have limitedsolubility in water such that less than about 2.0% by weight of theresin dissolves when placed in water. There are many types of oil-basedresins that are suitable for the present disclosure. Specific examplesof acrylic resins include, but are not limited to:

Curing

A person of ordinary skill in the art will also recognize that variousmethods may be used to cure resins in the present disclosure. Desirably,the curing occurs in situ in the presence of one or more metalcontaining materials in order to form polymeric materials with metallicnanoparticles.

In some embodiments, curing occurs by treating a resin with a chemical(i.e., chemical curing). In more specific embodiments, the resin istreated with one or more initiators, desirably in the presence of one ormore metal containing materials. Non-limiting examples of suitableinitiator systems include benzoyl peroxide (BPO) anddimethylparatoluidine (DMPT), and allyl thiourea (T) and cumenehydroperoxide (CH).

Initiators may be used at various concentrations and ratios for chemicalcuring. For instance, in some specific embodiments, chemical curing mayconsist of treating resins with allyl thiourea (T) and cumenehydroperoxide (CH). In other embodiments, chemical curing may consist oftreating resins with benzoyl peroxide (BPO) and dimethylparatoluidine(DMPT).

In other embodiments, curing can occur by treating resins with a lightsource, such as ultraviolet or blue light (i.e., light curing). In otherembodiments, curing may entail both light curing and chemical curing.Other methods of curing resins can also be envisioned by a person ofordinary skill in the art.

Applications

A person of ordinary skill in the art will recognize that the methods ofthe present disclosure can be used in various embodiments to formnumerous anti-microbial resin compositions. For instance, in someembodiments, the methods of the present disclosure can be used togenerate polymeric materials with silver nanoparticles (AgNP) by curingPMMA in the presence of silver benzoate (AgB).

FIG. 1 shows the change in color of a silver benzoate solution whencombined with a solvent, dimethylaminoethyl methacrylate (DMAEMA) overtime. As soon as the silver benzoate is added to DMAEMA, the solutionappears clear at first (A) and then proceeds to become darker over time(B).

FIG. 2 shows the change in color of a catalyst resin containing theself-cure amine upon addition of silver benzoate combined with DMAEMA.Initially, the catalyst resin with amine is clear in appearance, butbecomes darker with the addition of silver benzoate in DMAEMA.

FIG. 3 shows the darkening and spontaneous self-polymerization of acatalyst resin containing silver benzoate combined with DMAEMA inaccordance with methods of the invention. Over time, the catalyst resinwith the addition of silver benzoate darkens and eventually polymerizes.FIG. 4 shows the initial color of the base resin with benzoyl peroxide(A), the catalyst resin that contains photoinitiators for the dual-cureresin (B), and when the silver benzoate containing DMAEMA is added tothe catalyst resin (C);

FIG. 5 shows the color shift of the resin over time after the mixture ofsilver benzoate containing DMAEMA and the catalyst resin is mixed withthe base resin and polymerized at the time of mixing (A); after 30seconds (B); and after less than one (1) minute (C), while FIG. 6 showsa sample of the resin after polymerization is complete. FIGS. 5-6demonstrate the color shift of the resin after the mixture of silverbenzoate containing DMAEMA and the catalyst resin is mixed with the baseresin and polymerized.

FIG. 7 shows the color profile of various resin compositions prepared byadding the silver benzoate/DMAEMA mixture to the catalyst resin portionbefore mixing with the base resin portion to polymerize. The dark colorof the final product is directly correlated with the amount of silverpresent.

FIG. 8 shows the color profile of various resin compositions prepared byadding the silver benzoate/DMAEMA mixture to the base resin portion—thatwhen the silver benzoate/DMAEMA mixture is added to the base resin(instead of the catalyst resin), there is minimal color shift. When thephotoinitiator is added, the color shifts more. After 24 hours, there isa slight color shift but it is significantly reduced compared tospecimens where the silver benzoate/DMAEMA mixture is added to thecatalyst resin.

FIG. 9 compares the resin compositions of FIG. 7 (A) with the colorprofiles of various resin compositions prepared with the silverbenzoate/DMAEMA mixture added to the base resin before mixing with thecatalyst resin to polymerize and cured by either light-curing orself-curing (B). The self-cured resins show how mixing the silverbenzoate/DMAEMA mixture into the base resin instead of the catalystresin greatly reduces the initial color of the resin samples.Additionally, after 24 hours, the color shift is not significant. Thelight-cured resins are significantly darker than the self-cured resinsbut still less-colored than resins prepared with the silverbenzoate/DMAEMA mixture added to the catalyst resin. FIG. 10demonstrates the effects of light on resin samples in the dark (A) andin the light (B). FIG. 11 demonstrates the effects of light on resinsamples in the light (A) and in the dark (B). FIGS. 10-11 demonstratethat exposure to light will continue to darken the resin even if thesilver benzoate/DMAEMA mixture is added to the base resin.

FIG. 12 demonstrates the reduced color shift of various resincompositions that are self-cured, and stored in the dark prepared inaccordance with embodiments of the claimed invention.

Desirably, the methods of the present disclosure occur in situ. It isenvisioned that curing resin compositions in situ can lead to moreeffective polymerization with improved nanoparticle dispersion, therebyproducing more effective antimicrobial compositions.

An embodiment of the invention is directed to a method of making anantimicrobial resin composition containing silver nanoparticles, byselecting a silver-containing material, an acrylic resin monomer and asolvent that is miscible with the metal-containing material and with theacrylic resin monomer; combining the silver-containing material with thesolvent to form a silver-containing material solution; mixing thesilver-containing material solution with the acrylic resin monomer insitu to form an acrylic resin monomer solution; forming silvernanoparticles within the acrylic resin monomer solution by curing theacrylic resin monomer solution, wherein the curing process converts theacrylic resin monomer to a polymer; and forming an antimicrobial, resincomposition.

In certain embodiments of the invention, the synthesized resin may be adual cure resin or a self-cure resin that may be prepared using variouscombinations of resin monomers and suitable initiators. In variousembodiments, herein disclosed are self-cure and dual-cure resins withsilver nanoparticles that exhibit one or more of reduced color, reducedcolor shift, and/or reduced degree of self polymerization. In certainembodiments, compositions of the present invention comprise acamphorquinone (CQ) and 2-dimenthylaminoethyl methacarylate (DMAEMA). Inother embodiments of the invention, other photo initiators andco-initiators such as iodomium initiators may also be used.

Embodiments of the claimed invention are directed to methods for makingan antimicrobial resin composition containing silver particles andhaving a low initial color and reduced color shift over time. In orderto achieve a final resin composition having low initial color andreduced color shift, the manner in which the polymerization is carriedout is important. Typically, an antimicrobial resin compositioncomprising silver is prepared by combining a resin monomer with asolvent and an appropriate polymerization initiator along with asilver-containing material. However, depending upon the method, time andorder of addition of the silver-containing material, the color profileof the final resin composition is affected.

In an embodiment of the invention, the silver-containing material ismixed with a solvent and added to the acrylic base resin component thatdoes not contain an amine compound that exhibits a catalytic action, thelatter being a common component used in chemical (self) curedpolymerization systems. The base resin component used in this embodimentmay be a self-cure or dual-cure resin.

In a further embodiment of the invention, the mixing of thesilver-containing material with the base resin is carried out in the“dark” or under yellow light.

In a further embodiment of the invention, the silver-containing materialand base resin mixture is mixed with catalyst resin, which comprises acatalytic amine compound. The mixing of the base resin containing thesilver-containing material and the catalyst resin is preferably carriedout in the dark or under yellow light.

In an embodiment of the invention, the final cured resin composition isstored in the dark or under yellow light in order to prevent darkeningand extend the shelf life of the cured composition.

As is set forth in the figures, it is clear that the sequence ofaddition of the silver-containing material, i.e., adding it to the baseresin component relative to the catalyst resin component is critical fordetermining several properties of the final resin composition including,but not limited to, initial color of the resin composition, colorchanges exhibited by the resin composition over time upon storage andpremature spontaneous polymerization.

As shown in FIG. 1, a silver benzoate solution changes color over timewhen combined with a solvent, dimethylaminoethyl methacrylate (DMAEMA).FIGS. 4-6 demonstrate the color shift of the resin after silver benzoatecontaining DMAEMA is added to the catalyst resin followed by theaddition of this mixture to the base resin for initiation ofpolymerization. In contrast, FIG. 9 shows the color profiles of variousresin compositions prepared with the silver benzoate/DMAEMA mixtureadded to the base resin (instead of the catalyst resin) before mixingwith the catalyst resin to polymerize and cured by either light-curingor self-curing. The self-cured resins show how mixing the silverbenzoate/DMAEMA mixture into the base resin instead of the catalystresin greatly reduces the initial color of the resin samples.Additionally, after 24 hours, the color shift is not significant.

In accordance with an embodiment of the invention, FIG. 8 shows thatwhen the silver benzoate/DMAEMA mixture is added to the base resin,there is minimal color shift. When the photoinitiator is added, thecolor shifts more. After 24 hours, there is a slight color shift but itis significantly reduced compared to specimens where the silverbenzoate/DMAEMA mixture is added to the catalyst resin prior to mixingwith the base resin. FIG. 8 also shows that when the silverbenzoate/DMAEMA mixture is added to the base resin, it does notspontaneously polymerize as it does when added to the catalyst resin(compare to FIG. 3).

In accordance with an embodiment of the invention, FIG. 12 demonstratesthat when the resin compositions prepared in accordance with the methodsdescribed herein are both prepared and stored in the dark, they exhibitreduced color shift.

From the foregoing detailed description of specific embodiments of theinvention, it should be apparent that novel antimicrobial polymericmaterials and novel methods of making such materials have beendisclosed. Although the invention has been described with reference tospecific embodiments, these descriptions are not meant to be construedin a limiting sense. Various modifications of the disclosed embodiments,as well as alternative embodiments of the invention will become apparentto persons skilled in the art upon reference to the description of theinvention. It should be appreciated by those skilled in the art that theconception and the specific embodiment disclosed may be readily utilizedas a basis for modifying or designing other structures for carrying outthe same purposes of the present invention. It should also be realizedby those skilled in the art that such equivalent constructions do notdepart from the spirit and scope of the invention as set forth in theappended claims. It is therefore contemplated that the claims will coverany such modifications or embodiments that fall within the true scope ofthe invention.

What is claimed is:
 1. A method of forming an antimicrobial resincomposition containing silver nanoparticles, said method comprising:selecting a silver-containing material, an acrylic resin monomer and asolvent that is miscible with the silver-containing material and withthe acrylic resin monomer; combining the silver-containing material withthe solvent to form a silver-containing material solution; mixing thesilver-containing material solution with the acrylic resin monomer insitu to form an acrylic resin monomer solution that does not contain acatalytic amine; mixing a catalytic resin component that comprises acatalytic amine with the acrylic resin monomer solution; curing theacrylic resin monomer solution, wherein the curing process converts theacrylic resin monomer to a polymer; and forming an antimicrobial, resincomposition.
 2. The method of claim 1, wherein said silver-containingmaterial is silver benzoate.
 3. The method of claim 1, wherein saidacrylic resin is bisphenol glycidyl methacrylate (Bis-GMA), a bis-GMAanalog, poly (methyl methacrylate) (PMMA), Poly(benzyl methacrylate),Poly(butyl methacrylate), Poly(tert-butyl methacrylate), Poly(butylmethacrylate-co-isobutyl methacrylate), Poly(butylmethacrylate-co-methyl methacrylate), Poly(cyclohexyl methacrylate),Poly[(2-ethyldimethylammonioethyl methacrylate ethylsulfate)-co-(1-vinylpyrrolidone)], Poly(ethylene-co-glycidylmethacrylate), Poly(lauryl methacrylate-co-ethylene glycoldimethacrylate), Poly(octadecyl methacrylate), andPoly(1-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate).
 4. Themethod of claim 1, wherein said curing comprises a redox chemical curingprocess.
 5. The method of claim 1, wherein said curing comprises achemical curing process.
 6. The method of claim 1, wherein said curingcomprises a combination of light curing and chemical curing.